2-amino-4-tertiary butylamino-1,3,5-triazines

ABSTRACT

2-Amino-4-tertiary butylamino-1,3,5-triazines possessing in the 6-position a chlorine atom, a methoxy or a methyl-mercapto group are very effective weed killers and plant influencing agents.

United States Patent Nikles [451 July 11, 1972 [54] 2-AMINO-4-TERTIARYBUTYLAMINO- 1,3,5-TRIAZINES [72] Inventor; Erwin Nikles, Liestal,Switzerland [73] Assignee: Ciba-Geigy AG, Basel, Switzerland 22 Filed:April 16, 1970 21 Appl. No.: 29,252

[5 6] References Cited UNITED STATES PATENTS 2,909,420 10/1959 Gysin etal. ..260/249.8

Primary Examiner-John M Ford Attorney-Harry Goldsmith, Joseph G. Kolodnyand Mario A. Monaco [5 7] ABSTRACT 2-Amino-4-tertiarybutylamino-1,3,5-triazines possessing in the 6-position a chlorine atom,a methoxy or a methyl-mercapto group are very effective weed killers andplant influencing agents 4 Claims, No Drawings 2-AMlNO-4-TERTIARYBUTYLAMINO- l ,3,5-TRIAZINES This invention relates to substituted1,3,5-triazines and to herbicidal preparations containing them.

The present invention provides compounds of the general formula in whichX represents a chlorine atom, a methoxy group or a methylthio group, ifdesired, in combination with a suitable carrier or distribution medium,for example, a solvent, diluent,

suspending agent, emulsifying agent, wetting agent, adhesive andthickener, or other important active substances used in agriculture.

The herbicidal preparations according to the present inventionpreferably contain from 0.1 to 95 per cent by weight of the activeingredient.

The new herbicidal preparations ensure better control of grass weeds andother weeds in crops than the hitherto known 1,3,5-triazines, forexample, in sugar cane, potatoes, rice, maize, peas, sugar beet, cotton,ground nut, plants of the cabbage family, grain and carrot. They canalso be used in orchards and vineyards.

The rate of'application is of the order of 0.2 to 6 kg AS/hectare,preferably 0.3 to 4 kg AS/hectare.

The compounds of the present invention are eminently suitable both forthe selective control and extermination of weeds in crops and the totalextermination and prevention of undesired plant growth. The term weedsis used herein to include previously cultivated crop plants that areundesired. The compounds defined above also have other inhibitoryeffects on plant growth. In particular, they act as defoliants, forexample, in the case of the cotton plant. They accelerate ripening bycausing premature drying out, for example, in the case of the potatoplant. They also decrease fruit development, delay blossoming, prolongthe harvesting period and improve the storage properties of theharvested crop. Growth inhibiting compounds can be used to improve cropyield not only by suppression of weed growth, but also by counteringinfluences that could stimulate the growth of crops in an undesirabledirection, for example, high temperatures or excessive use offertilizers. On the other hand, the use of herbicidal preparations forthe extermination of stubborn weed growth can also be useful on along-term basis when the preparations are not sufficiently selective toprevent a reduction in crop yield at the time of application.

The preparations of the present invention for influencing plant growthand combating weeds can be made up in the form of, for example,solutions, emulsions, suspensions or dusting preparations. The form ofthe preparation depends on its ultimate use. The essential feature of apreparation in respect of its physical form is that it should ensurefine dispersion of the active ingredient. The effect of the activeingredient can be reinforced by the use of carriers that are themselvesphytotoxic, for example, high-boiling mineral oil fractions orchlorinated hydrocarbons, this applying especially to the totalextermination of plant growth, premature drying out and defoliation. Onthe other hand, selectivity in respect of growth inhibition tends toassert itself more when inert carriers are used, this applying, forexample, to the selective control of weeds.

The solvents used for the preparation of solutions are, especiallyalcohols, for example, ethyl alcohol and isopropyl alcohol, ketones, forexample acetone and cyclohexanone, aliphatic hydrocarbons, for example,kerosene, cyclic hydrocarbons, for example, benzene, toluene, xylene andtetrahydronaphthalene, alkylated naphthalenes, chlorinated hydrocarbons,for example, tetrachloroethane and ethylene chloride, as well as mineraland vegetable oils, and mixtures of these substances.

The aqueous preparations are preferably in the form of emulsions anddispersions. The active substances may be homogenized in water eitherper se or in one of the abovementioned solvents, preferably with the aidof a wetting or dispersing agent. Quaternary ammonium compounds areexamples of suitable cationic emulsifying or dispersing agents. Suitableanionic substances are, for example, soaps, soft soap, aliphaticlong-chain sulphuric acid monoesters, aliphatic-aromatic sulphonic acidsand long-chain alkoxy-acetic acids, and non-ionic emulsifying ordispersing agents are polyethylene ethers of fatty alcohols andpolyethylene oxide condensation products. On the other hand, it is alsopossible to use concentrates consisting of the active ingredient,emulsifier or dispersant and, if necessary, solvent. Concentrates ofthis kind can be diluted with water prior to use.

Dusting preparations can be prepared by mixing the active ingredientwith a solid carrier, or by grinding the two together. Suitable carriersare, for example, talcum, diatomaceous earth, kaolin, bentonite, calciumcarbonate, boric acid and tricalcium phosphate, and also wood flour,cork meal, charcoal and other materials of vegetable origin. On theother hand, the substances can be absorbed on to the carrier in avolatile solvent. Pastes and preparations in powder form can be renderedcapable of suspension in water by the addition of wetting agents andprotective colloids and used as sprays.

Since the preparations of the present invention include both solid andliquid substances having virtually the same herbicidal action, it issimple to prepare liquid concentrates for aqueous emulsions and alsopowder or paste concentrates for aqueous suspensions which have a highconcentration of active ingredient.

Granulates can be prepared in an especially simple manner by dissolvinga compound of the general formula I in an organic solvent, allowing thesolution to be taken up by a granulated material, for example,attapulgite, SiO granulated calcium, bentonite, and the like, and thenevaporating the organic solvent.

Polymer granulates can also be used. These can be prepared by mixing acompound of the general formula I with polymerizable compounds, forexample urea/formaldehyde, dicyanodiamide/formaldehyde andmelamine/formaldehyde, and then carrying out polymerization under mildconditions that do not affect the active substances; granulation can becarried out simultaneously. A more advantageous method is to impregnateprepared porous polymer granulates for example, urea/formaldehyde,polyacrylonitrile and polyesters, having a specified surface area and apredetermined adsorption/desorption ratio with the active substances,for example, in the form of solutions (in a low-boiling solvent) andthen to remove the solvent.

Polymer granulates of the kznd specified can also be applied in the formof microgranulates preferably having a bulk density of from 300grams/liter to 600 grams/liter by means of atomizers. The dusting oflarge areas of grain crops can be carried out from aircraft.

Other pesticides fertilizers, surfactants or substances to increase thespecific gravity, for example, BaSO can, of course, be added to thegranulates.

Granulates can also be obtained by compacting the carrier material withthe active substance and other additives and then comminuting themixture.

The preparations in their various forms may also contain the usualadditives that improve dispersion, adhesion, rain-resistance and, ifnecessary, penetrating power; substances of this kind are, for example,fatty acids, resins, wetting agents, glues, casein and alginates. Theirspectrum of biological action can be broadened by the addition ofsubstances having bactericidal or fungicidal properties or that may alsoinfluence plant growth; fertilizers may also be added.

Known weed-killers may also be added to reinforce the action of thepreparations of the invention or to increase their spectrum ofbiological action.

Examples of such substances are as follows:

Substituted ureas, for example, N-phenyl-N,N-dimethylurea,N-(4-chloropheny1)-N,N'-dimethylurea, N-(3,4-dichlorophenyl)-N',N'-dimethylurea, N-(4-chlorophenyl)-Nmethoxy-N-methylurea, N-(3,4-dich1oropheny1)-N-methoxy-N-methylurea,N(4-bromophenyl)-N'-methoxy-N'- methylu'rea,N(4-bromo-3-chlorophenyl)-N'-methoxy-N- methylurea,N(4-chloropheny1)-N'-methyl-N-butylurea,N(4-chlorophenyl)-N-methyl-N'-isobutylurea and N(-chlorophenoxyphenyl)-N,N'-dimethylurea;

Substituted triazines, for example, 2-chloro-4,6-bis-(ethy1amino)-s-triazine,2-chloro-4-ethylamino-6-isopropylamino-s-triazine,2-ch1oro-4,6-bis(methoxypropy1amino)-striazine,2-methoxy-4,6-bis(isopropylamino)-s-triazine, 2-diethylamino-4-isopropylacetamido-6methoxy-s-triazine, 2-isopropylamino-4-methoxyethylamino-o-methyl-mercapto-striazine,2-methylmcrcapto-4,6-bis(isopropylamino)-striazine,2-methylmercapto-4,6-bis-( ethylamino)-s-triazine, 2-methylmercapto-4-ethylamino-6-isopropylamino-s-triazine, 2-methoxy-4,6-bis(ethy1amino)-s-triazine, 2-methoxy-4-ethylamino-6-isopropylamino-s-triazine and 2-chloro-4,6-bis(isopropylamino)-s-triazine; (these triazines can be mixed with thecompounds of general formula I in ratios of from 1 10 to l Phenols, forexample, dinitro-sec.-buty1pheno1 or the salts thereof andpentachlorophenol or the salts thereof;

Carboxylic acids, for example, 2,3,6-trichlorobenzoic acid and salts,2,3,5,6-tetrachlorobenzoic acid and salts,2-methoxy-3,5,6-trichlorobenzoic acid and salts, 2-methoxy-3,6-dichlorobenzoic acid and salts, 3-amino-2,S-dichlorobenzoic acid andsalts, 3-nitro-2,5-dich1orobenzoic acid and salts, 2-methy1-3,fi-dichlorobenzoic acid and salts, 2,4- dichlorophenoxyaceticacid and salts and esters, 2,4,5- trichlorophenoxyacetic acid and saltsand esters, (2-methyl-4- chlorophenoxy)acetic acid and salts and esters,2-(2,4,5- trichlorophenoxy)propionic acid and salts and esters, 2-(2,4,5-trichlorophenoxy)ethyl-2,2'-dichloroproprionate, 4-(2,4-dichlorophenoxy)butyric acid and salts and esters and 4-(2-methyl-4-chlorophenoxy)butyric acid and salts and esters;

Carbamic acid derivatives, for example, carbanilic acid isopropylester,meta-chlorocarbanilic acid isopropylester,

meta-chlorocarbanilic acid-4-ch1oro-2-butinylester andmetatrifluoromethylcarbanilic acid isopropylester; and

Various other compounds, for example, 2,3,6-

trichlorophenylacetic acid, chloroacetic acid diallylamide, maleic acidhydrazide, sodium salt of methylarsonic acid, borates, 3-aminotriazole,pyrazine derivatives, for example, pyramine, endooxohexahydrophthalicacid, diphenylacetonitrile, Treflan, N-methoxymethylene-N-chloroacetyl-2,6-diethy1ani1ine, Balan, Planavin, tetrachlorophthalic aciddimethylester, 4-trifluoromethyl-2,4'-dinitrodiphenylether,2,4-dich1oro-4-nitrodiphenylether, 3-cyclohexyl-6-methyluracil, 3cyclohexy1-6-sec.-buty1uraci1, 3-cyclohexy1-5-bromouracil,3--cyc1ohexy1-5-chlorouracil, 3-isopropy1-5chlorouraci1,3-isopropyl-5-bromouracil, and other known uracils.

The parts and percentages in the following manufacturing examples are byweight.

EXAMPLE 1 2-Amino-4-tertiary butylamino-6-chlor0-1,3,5-triazine 330parts of 2-amino-4,6-dich1oro-1,3,5-triazine were suspended in 3,000parts by volume of toluene. 300 parts of tertiary butylamine were addeddropwise to the suspension at 10 C and the batch stirred for 14 hours at40? C. The precipitate that formed was removed by filtration, thefiltrate concentrated to a small volume and allowed to stand.

The product that crystallizes out was isolated by filtration and washedwith toluene and hexane. Melting point: 145 146 C.

EXAMPLE 2 2-Amino-4-tertiary butylamino-o-methoxy-l ,3,5-triazine Asodium methylate solution was prepared from 38 parts of sodium and 1,800parts by volume of methanol. 302 parts of the 2-amino-4-tertiarybuty1amino-6-chloro-l,3,5-triazine prepared in accordance with Example 1were added to the solution at room temperature.

The mixture was refluxed for 24 hours and then diluted with 4,000 partsof water.

The finely crystalline product was isolated by filtration, washed withwater and dried. Melting point: 138 140 C.

EXAMPLE 3 2-Amino-4-tertiary butylamino-o-methylmercapto-1,3,5- triazineA sodium isopropylate solution was prepared from 38 parts of sodium and1,500 parts by volume of isopropanol. parts of methylmercaptan were runinto the solution at 0 C. 302 parts of the 2-amino4-tertiarybutylamino-6-chloro-1,3,5- triazine prepared in accordance with Example1 were then introduced and the mixture kept at 80 C for 14 hours. Thebatch was then diluted with 3,000 parts of water, cooled, and theprecipitate isolated by filtration.

The colorless product was washed with water. Melting point: 142- 144 C.

EXAMPLE 4 Wettable powders A Wettable powder was prepared by mixing andfinely grinding the following components. The powder is soluble inwater.

50 parts of an active ingredient according to the present invention,

20 parts of highly adsorptive silica 25 parts of Bolus alba (kaolin) 15parts of sodium l-benzy1-2-stearylbenzimidazole-6,3'-

disulphonate 3.5 parts of the reaction product derived from paratertiaryoctylphenol and ethylene oxide.

Emulsion concentrates a. A mixture was prepared from 40 parts of acompound of the general formula I and 10 parts of a mixture comprisingan anionic surface-active compound, preferably the calcium or magnesiumsalt of monolaurylbenzenemonosulphonic acid, and a non-ionicsurface-active compound, preferably a polyethyleneglycol ether ofmonosorbitollaureate, and the whole dissolved in a small amount ofxylene. The batch was bulked to ml with xylene, and a clear solutionobtained that can be used as a spray concentrate. A stable emulsion isproduced by the addition of water.

b. An emulsion concentrate can also be formulated according to thefollowing procedure when active ingredients having good solubility areused:

20 parts of active ingredients,

70 parts of xylene and 10 parts of a mixture comprising the reactionproduct obtained from an alkylphenol and ethylene oxide, and calciumdodecylbenzenesulphonate are mixed. An emulsion suitable for sprayingcan be obtained by diluting the mixture to the desired concentrationwith water.

Granulates a. 7.5 parts of one of the compounds of the general formula 1were dissolved in 100 ml of acetone, and the solution obtained added to92 grams of granulated attapulgite (mesh size: 24/28 meshes per inch).The batch was well mixed and the solvent removed in a rotary evaporator.A

granulate having an active substance content of 7.5 percent wasobtained.

A percent polymer granulate was obtained by dissolving from 1,050 to1,100 grams of a compound of the general formula I in 2 liters oftrichloroethylene and spraying the solution on to 9,230 grams of porousurea/formaldehyde granulate in a fluidized bed granulator at a pressureof 1.5 atmospheres gauge. The solvent was removed by raising thetemperature of the fluidization air to about 50 C.

c. A 7.5 percent weighted granulated was obtained by compressing andmixing 770 grams of a compound of the general formula I, 500 grams ofBaSO 1,000 grams of urea and 7,730 grams of porous polyacrylonitrilepowder on a roller mill and then breaking up the material to the desiredgrain size.

EXAMPLE 5 Method:

Plant seeds were sown in a series of earthenware pots in a greenhouse.

In the preemergent test, the soil was sprayed with a given concentrationof a spray prepared in accordance with the formulation example one dayafter sowing.

In the postemergent test, treatment was carried out with the same sprayabout 10-12 days after sowing when the plants were in the two-leaf orthree-leaf stage.

Assessment is made 20 days after sowing.

The results of the tests are given in the following tables, comparisonbeing made between the triazines of the present invention and the known1,3,5-triazines that are most closely related chemically.

1. Compound 1 compared with 2-amino-4-isopropylamino-6-methylmercapto-l,3,5-triazine (A) and 2-ethylamino-4-isopropylamino-G-chlorol ,3 ,5-triazine Compound I shows a distinctlybroader spectrum of action as a weed killer than the known Compound Awithout any damage to the maize crop. The commercial product ATRAZIN iscompletely innocuous towards Digitaria, one of the most important fieldweeds, whereas Compound I totally destroys this weed at both rates ofapplication (2 kg/hectare and l kg/hectare).

2. Compound 2 compared with 2-amino-4-isopropylamino-6- chloro- 1,3,5-triazine (B) Postemergent treatment Compound 2 Compound B (known)kgAS/hectare 3 1.5 0.75 3 1.5 0.75

Avena 9 9 8 9 7 7 Zea mays 2 l 1 l l l Digitaria 9 6 3 4 3 l Poa 9 9 9 76 4 Alapecurus 9 9 9 9 8 6 Galium 9 9 9 9 8 4 Calendula 9 9 9 9 9 3Chrysanthenum 9 9 9 9 9 9 Ipomoea 9 9 9 9 9 7 Compound 2 shows adistinctly broader spectrum of action as a weed killer than the knownCompound B.

Preemergent treatment compound 2 compound B (known) kgAS/hectare 3 1.5L5

Avena 9 9 9 8 Zea may: 2 I 3 2 Par: 9 9 9 8 Alopecurus 9 9 9 7 Galium 98 7 5 Calendula 9 9 9 9 Chrysanthenum 9 9 9 9 Ipomoea 9 9 9 9 In thepreemergent treatment, the selective herbicidal action of Compound 2 ismuch better than that of the control Compound B.

3. Compound 3 compared with 2-amino-4-isopropylamino-6-methoxy-1,3,5-triazine (PROMETRYN) Preemergent treatment When compound 3is used in cotton (Gossypium) as compared with PROMETRYN, the knownproduct shows much less selectivity than the compound of the invention.

I claim:

1. A compound of the general formula in which X represents a chlorineatom, a methoxy group or a methylthio group.

2. A compound according to claim 1 in which X is chlorine.

3. A compound according to claim 1 in which X is a methoxy group.

4. A compound according to claim 1 in which X is a methylthio group.

lOlO44 0190

2. A compound according to claim 1 in which X is chlorine.
 3. A compoundaccording to claim 1 in which X is a methoxy group.
 4. A compoundaccording to claim 1 in which X is a methylthio group.